Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
  • C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters

Definitions

• Methacrolein is produced by heating a diacetoxyisobutene together with water in the presence of an acid and distilling off resulting methacrolein.
• the methacrolein is formed by hydrolysis coupled with separation of acetic acid.
• the present invention relates to the production of methacrolein.
• Methacrylic acid for example, can be produced by oxidizing methacrolein.
• Various processes for the production of methacrolein have already been described. Some of these earlier processes produce unsatisfactory yields and some other processes fail to be commercially attractive procedures because of the use of too costly starting material therein.
• the process of the present invention now permits the production of methacrolein in especially high yields from diacetoxyisobutenes, which in turn can readily be produced from methallyl acetate, as reported in German published Applications 1945528 and 1945529.
• German published Application 1964085 describes a process, wherein isobutene, acetic acid and molecular oxygen are reacted in contact with a palladium catalyst to produce methallyl acetate in good yields.
• CHzOOCOHa 2-methylene-1,3diacet0xypr0pane contains more than 90% of Z-methylene-1,3-diacetoxypropane as its principal fraction.
• methacrolein is obtained substantially in quantitative yield.
• CH (
• the present invention relates more particularly to a process for making methacrolein, comprising heating a diacetoxyisobutene together with water in the presence of an acid and distilling off resulting methacrolein, this latter compound being formed by hydrolysis coupled with separation of acetic acid.
• diacetoxyisobutene for the diacetoxyisobutene to be selected from 2- methyl-3,3-diacet0xypropene-(1), 2 methyl-1,3-diacetoxypropene-(l), Z-methylene-1,3-diacetoxypropane or a mixture thereof;
• the acid for the acid to be selected from sulfuric acid, phosphoric acid, an organic sulfonic acid or phosphonic acid, and for the acid to be used in a proportion of between 0.5 and 15 weight percent, based on the diacetoxyisobutene used;
• the zinc, cadmium, mercury or iron ions may be used in the form of metal salts, for example as sulfate (ZnSO CdSO HgSO Fe (SO to accelerate the hydrolysis to give methacrolein.
• ZnSO CdSO HgSO Fe SO to accelerate the hydrolysis to give methacrolein.
• the acetic acid formed during hydrolysis has an autocatalytic efiect upon the further hydrolysis of the bulk of diacetoxyisobutene used.
• the hydrolysis should conveniently be effected in a standard distilling column.
• the diacetoxyisobutenes are reflux heated, for example, together with water and a heavy metal salt in sulfate form.
• the heating step may be effected in the further presence of a mineral acid or organic sulfonic acid or phosphonic acid, which, however, should be introduced into the column prior to the reaction components.
• the useful organic sulfonic acids include, for example, p-toluene-sulfonic acid and benzene-sulfonic acid
• the useful phosphonic acids include alkylphosphonic acids having from 1 to 20 carbon atoms in the alkyl radical, alkenyl or arylphosphonic acids, e.g.
• ethyl or vinylphosphonic acid Theresulting methacrolein is continuously removed from the head of the column.
• a small proportion of a stabilizer, for example hydroquinone, should conveniently be added to the methacrolein removed from the column, more preferably to the material in the base of the distilling column, so as to avoid undesirable polymerization of methacrolein.
• EXAMPLE 5 The procedure was the same as that described in Example 1. HgSO was used but the sulfuric acid was omitted. The hydrolysis was found initially to proceed very reluctantly. It did accelerate, however, as the quantity of acetic acid increased, and it was complete after 24 hours. Methacrolein was produced in a yield of 98%, based on the theoretical.
• a process for the manufacture of methacrolein comprising reflux heating a diacetoxyisobutene together with water in the presence of an acid selected from the group consisting of sulfuric acid, phosphoric acid, acetic acid, p-toluene-sulfonic acid, benzene-sulfonic acid, ethyl phosphonic acid and vinylphosphonic acid, and distilling off resulting methacrolein.
• diacetoxyisobutene is selected from the group consisting of 2-methy1-3, 3-diacetoXypropene-(1), Z-methyl-l, 3-diacetoxypropene-(l), 2-methy1ene-1, B-diacetoxypropane and mixtures thereof.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=5787535

Family Applications (1)

Country Status (13)

Cited By (1)

Families Citing this family (2)

• 1970
  • 1970-11-09 DE DE19702054988 patent/DE2054988A1/de active Pending
• 1971
  • 1971-10-15 AU AU34646/71A patent/AU454606B2/en not_active Expired
  • 1971-10-19 CA CA125,486A patent/CA942321A/en not_active Expired
  • 1971-10-19 ZA ZA717006A patent/ZA717006B/xx unknown
  • 1971-10-27 GB GB4991571A patent/GB1323017A/en not_active Expired
  • 1971-10-29 NL NL7114959A patent/NL7114959A/xx unknown
  • 1971-11-05 AT AT955871A patent/AT311307B/de not_active IP Right Cessation
  • 1971-11-05 IT IT53880/71A patent/IT942280B/it active
  • 1971-11-08 BE BE775047A patent/BE775047A/xx unknown
  • 1971-11-08 US US00196806A patent/US3819715A/en not_active Expired - Lifetime
  • 1971-11-08 BR BR7425/71A patent/BR7107425D0/pt unknown
  • 1971-11-09 FR FR7140159A patent/FR2113719A5/fr not_active Expired
  • 1971-11-09 CH CH1632471A patent/CH561678A5/xx not_active IP Right Cessation

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